Condensation of aromatic compounds with unsaturated organic compounds in the presence of composite catalysts



United States Patent "cc CONDENSATION OF AROMATIC COMPOUNDS WITH UNSATURATED ORGANIC COMPOUNDS IN THE PRESENCE OF COMPOSITE CATALYSTS Herman Pines, Evanston, Ill., and Vladimir N. Ipatiefi, deceased, late of Chicago, 11]., by Vladimir Haensel, Hinsdale, Herman Pines, Evanston, and Vincetta Kibort, Chicago, Ill.,executors, assignors to Universal Oil Products Company, Des Plaines, 111., a corporation of Delaware No Drawing. Application June 7, 1954, Serial No. 435,031

14 Claims. (Cl. 260-668) This application is a continuation-in-part of our copending application Serial No. 219,314, filed April 4, 1951, now abandoned.

This invention relates to the condensation of unsaturated organic compounds with aromatic compounds and to products formed thereby. This invention relates more particularly to the side chain alkylation with an olefin of an alkylaromatic hydrocarbon in which a carbon atom combined with the aromatic nucleus is also combined with at least one hydrogen atom. The process relates more specifically to the side chain alkylation with ethylene of an alkylbenzene hydrocarbon having at least one hydrogen atom combined with a carbon atom in alpha position to the benzene ring.

The condensation of aromatic compounds with unsaturated organic compounds such as the alkylation of aromatic hydrocarbons with olefinic hydrocarbons, has been the subject of many investigations over a long period of time. Many different catalysts have been used including various mineral acids and acid-acting compounds but in all of these reactions, nuclear condensation has always been effected. Thus in the acid catalyzed alkylation of aromatic compounds having attached to a carbon atom of the ring a saturated carbon atom to which is attached at least one hydrogen atom, the entering alkyl group attaches to the aromatic nucleus. No direct catalytic method of introducing the alkyl group into the side chain has been known. Heretofore we accomplished side chain alkylation of toluene and related alkylaromatic compounds by noncatalyzed thermal means as set forth in our copending application Serial Number 152,991 filed March 30, 1950, now abandoned, but this thermal alkylation process requires high temperatures and high pressures for its successful operation.

We have now found that side chain alkylation of toluene and other carbocyclic aromatic and heterocyclic aromatic ring compounds having a nonolefinic double bond such as pyridine, quinoline, pyrrole, etc. and having attached to a nuclear carbon atom a saturated carbon atom to which is attached at least one hydrogen atom may also be used as starting materials to elfect side chain alkylation with an olefin at relatively lower temperatures and pressures in the presence of a catalyst comprising essentially an alkali metal and an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group and a cyano group. The carbon atom which is attached to the aromatic nucleus of said aromatic compounds is referred to as a saturated carbon atom be cause it is a part of a nonolefinic group such as an alkyl group, a cycloalkyl group, and an aralkyl group containing no ethylenic bonds or similar unsaturation. The carbon atom which is attached to an aromatic nucleus is 2,721,885 Patented Oct. 25, 1955 thus a part of a saturated group including an alkyl group and a cycloalkyl group, and an aralkyl group containing no olefinic unsaturation.

An object of this invention is to react an unsaturated organic compound with an aromatic compound selected from the group consisting of carbocyclic and heterocyclic aromatic ring compounds having attached to a nuclear carbon atom a nonolefinic or saturated carbon atom to which is attached at least one hydrogen atom.

An additional object of this invention is to react a monoolefin with an alkylaromatic hydrocarbon to form an aromatic hydrocarbon with a longer alkyl group.

Another object of this invention is to condense ethylene with the side chain of an alkylaromatic hydrocarbon having attached to a nuclear carbon atom a carbon atom of said alkyl group to which is attached at least one hydrogen atom.

Still another object of this invention is to condense ethylene with the alkyl side chain of an alkylbenzene hydrocarbon, said side chain containing an alpha carbon atom to which is attached a replaceable hydrogen atom.

A further object of this invention is to condense ethylene with the cycloalkyl group of a cycloalkylbenzene hydrocarbon, said cycloalkyl group having a hydrogen atom combined with the carbon atom of the cycloalkyl group which is attached to the aromatic ring.

A still further object of this invention is to provide a process for the side chain alkylation of an alkylaromatic hydrocarbon.

A further object of this invention is to condense ethylene with a polycyclic hydrocarbon having at least one of the rings saturated and having at least one hydrogen atom combined with the carbon atom of the saturated ring which is attached to the aromatic ring.

An additional object of this invention is to provide a method for producing an aromatic compound containing a long hydrocarbon side chain, said compound being useful in the production of detergents, wetting agents and the like.

One embodiment of this invention relates to a process which comprises reacting a nonconjugated olefinic hydrocarbon and an aromatic compound selected from the group consisting of carbocyclic aromatic and heterocyclic aromatic ring compounds having attached to a nuclear carbon atom a carbon atom of a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, a cycloalkalkyl group and an aralkyl group and to which last named carbon atom is attached at least one hydrogen atom, the process being carried out at condensation conditions in the presence of an alkali metal and of an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group, and recovering the resultant condensation product.

A second embodiment of this invention relates to a process Which comprises reacting a nonconjugated olefinic hydrocarbon and an aromatic compound selected from the group consisting of carbocyclic aromatic and heterocyclic aromatic ring compounds having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at condensation conditions in the presence of an alkali metal and of an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group.

Another embodiment of this invention relates to a process which comprises reacting a monoolefin and an aromatic compound having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at condensation conditions in the presence of an alkali metal and of an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoXyl group, a nitro group, and a cyano group.

Still another embodiment of this invention relates to a process for producing longer chain aromatic hydrocarbons which comprises reacting an alkene and an aromatic hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of an alkali metal and of an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group.

A further embodiment of this invention relates to a process for producing a longer chain benzene hydrocarbon which comprises reacting an alkene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of a catalyst comprising essentially sodium and an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroXyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group.

A still further embodiment of this invention relates to a process for producing a longer chain benzene hydrocarbon which comprises reacting ethylene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of a catalyst comprising essentially an alkali metal and an organic compound represented by the for mula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group, and recovering a longer chain benzene hydrocarbon from the resultant reaction product.

An additional embodiment of this invention relates to a process for producing a longer chain benzene hydro carbon which comprises reacting ethylene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of a catalyst comprising essentially sodium and an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group, and recovering the resultant reaction products.

A still additional embodiment of this invention relates to a process which comprises catalytically reacting a nonconjugated olefinic hydrocarbon and an aromatic com pound having a structure represented by the formula:

4 wherein Ar represents an aromatic radical having a nucleus selected from carbocyclic and heterocyclic nuclei and R and R each separately and independently represents a member of the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, and an aryl group and R and R together represent a cycloalkyl group, the process being carried out at a condensation temperature in the presence of a catalyst comprising essentially an alkali metal and an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group, and recovering the resultant condensation product.

Still another embodiment of this invention relates to a process for producing normal propylbenzene which comprises reacting ethylene and toluene at a condensation temperature in the presence of a catalyst comprising essentially sodium and an organic hydroxy compound, and recovering the resultant condensation product.

Another embodiment of this invention relates to a process for producing normal propylbenzene which comprises reacting ethylene and toluene at a condensation temperature in the Presence of a catalyst comprising essentially sodium and an organic nitro compound, and recovering normal propylbenzene from the resultant reaction product.

An additional embodiment of this invention relates to a process for producing normal propylbenzene which comprises reacting ethylene and toluene at a condensation temperature in the presence of a catalyst comprising essentially sodium and an organic acid, and recovering normal propylbenzene from the resultant reaction product.

A still further embodiment of this invention relates to a process for producing normal propylbenzene which comprises reacting ethylene and toluene at a condensation temperature in the presence of a catalyst comprising essentially sodium and a branched chain alcohol, and recovering normal propylbenzene from the resultant reaction product.

The compounds with which unsaturated organic compounds are condensed in our process comprise aromatic compounds having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group to which last named carbon atom is attached at least one hydrogen atom. By the term aromatic compound we mean to include not only benzene, substituted benzenes, naphthalenes, and derivatives thereof, but also all compounds containing a stable ring or nucleus such as is present in enzene and which possesses unsaturation in the sense that benzene does, but which has no ethylenic unsaturation. Consequently it can be seen that the term aromatic compound, in the sense in which it is used in the specification and the appended claims, includes not only carbocyclic compounds but also heterocyclic compounds having stable nuclei. The carbocyclic compounds may have a benzene, naphthalene, etc. nucleus. The heterocyclic aromatic compounds may have a pyridine, furan, thiophene, pyrrole, pyrazole, etc., nucleus. In addition, the aromatic compounds contemplated for use in our process may contain both a carbocyclic ring and a heterocyclic ring such as is found in indole and in carbazole. Also, the aromatic compounds may contain both a benzene nucleus and a cycloalkane nucleus such as is found in tetralin and in indan.

As hereinbefore stated, the aromatic compounds preferred for use in our process contain a saturated side chain, said chain being attached to a nuclear carbon atom by a saturated carbon atom, i. e., a carbon atom that is bonded by univalent bonds to four atoms. The saturated carbon atom should have at least one hydrogen atom attached thereto. These requisites are desirable for the reason that aromatic compounds such as t-butylbenzene, which do not have a hydrogen atom attached to the alpha Carbon atom, show very little tendency under the conditions of operation employed in our'process to undergo condensation of the type herein taught. Similarly, styrene, in which the alpha carbon atom in the side chain is unsaturated, does not condense with unsaturated organic compounds in the manner herein specified. Thus the preferred aromatic compounds are those in which the alpha carbon atom of the side chain is saturated and in which said alpha carbon atom has at least one hydrogen atom attached thereto. The side chain may comprise only one carbon atom, as the methyl group in toluene, or it may comprise a number of saturated carbon atoms in straight chain or branched chain relation such as the normal butyl radical or the isobutyl radical in normal butylbenzene and isobutylbenzene, respectively. The substituent need not necessarily be an aliphatic chain; it may be a cycloalkane radical as in tetralin or as in cyclohexylbenzene and an aralkyl side chain as a benzyl group in diphenylmethane.

Suitable alkylaromatic hydrocarbons include toluene, ethylbenzene, normal propylbenzene, cumene, normal and secondary butylbenzene, methylnaphthalene, and the like. Other suitable aromatic hydrocarbons include tetralin, indan, diphenylrnethane, cyclopentylbenzene, and methylethylbenzene.

The aromatic reactants employed in our process are condensed with nonconjugated unsaturated organic compounds. The unsaturated organic compounds are olefinic in character and include monoolefins and particularly ethylene. For the purposes of this invention, aromatic compounds such as benzene are not regarded as being unsaturated. Examples of unsaturated organic compounds suitable for use in this process include monoolefins such as ethylene, propylene, l-butene, Z-butene, and isobutylene; monoolefins of higher molecular weight; nonconjugated dienes, such as 2,5-dimethyl-1,5-hexadiene, and nonconjugated polyolefins containing more than two pairs of double bonds per molecule; unsaturated ketones such as mesityl oxide, and compounds such as allyl amine, allyl cyanide, acrylonitrile, alpha-cyanoacrylonitrile and the like.

Catalysts which are useful in this process include a combination of an alkali metal or alkali metals and at least one organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group and a cyano group. Of the alkali metals: lithium, sodium, potassium, rubidium, and cesium, the more plentiful sodium and potassium are generally preferred and particularly sodium because of its relatively lower cost. These alkali metals are utilized together with the organic compounds represented by the formula RX as indicated hereinabove. The RX compounds thus include alcohols, particularly branched chain alkanols and also hydroxy aryl compounds such as phenols and various alkyl phenols including phenol, cresols, xylenols, etc. Carboxylic acids which are utilized with alkali metals as catalyst for this process include particularly aromatic monocarboxylic acids such as benzoic acid, toluic acid, etc. Nitrobenzene and other nitroaromatic hydrocarbons and nitroalkanes are also combined with alkali metals to form effective catalysts for the process. The cyano compounds include CsHsCN. In general an excess of the alkali metalis employed relatively to the RX compound also present in the catalyst mixture.

Better contacting of the reactants and catalysts and improved yields of desired products are sometimes effected by mixing the alkali metal and organic compound RX catalyst mixture with a catalyst supporting or spacing material such as activated charcoal; also granular coke, silica, alumina, pumice, porcelain, quartz, etc.; steel turnings; copper shot, etc. which do not have an adverse influence on the reaction but improve the mixing. Such spacing materials are useful-in-eit'her batch type operation as in an autoclave or in continuous treatment in a tubular reactor or other suitable apparatus.

The process of this invention is carried out using either batch or continuous types of operation in suitable equipment such as autoclaves or tubular reactors constructed from steel or glass lined steel reactors. The process is carried out at a temperature of from about to about 350 C. and preferably at a temperature of from about 150 to about 275 C. at a pressure of from about 5 to about 50 atmospheres. When the stirring or mixing of the reactants and catalyst is very thorough and eflicient, the process may be carried out readily at a temperature of C. and at a pressure of 5 atmospheres, but higher temperatures and pressures are preferred when the mixing is less efficient. The operating temperatures and pressure will also be dependent upon the aromatic and olefinc hydrocarbons charged and upon the ratios of reactants present in the reaction zone, as well as upon the catalyst present.

In order to promote the primary side chain alkylation that is to attach only one alkyl group to the alkyl side chain and in some instances to decrease the loss of olefin through undesired side reactions, it is generally preferred to employ an excess of aromatic hydrocarbon to olefin such as ethylene in this process. In other words, the preferred ratio of aromatic hydrocarbon to olefinic hydrocarbon is greater than one.

The amount of catalyst used in the process is dependent upon the nature and reactivity of the aromatic hydrocarbon undergoing side chain alkylation and upon the nature of the olefin used as alkylating agent. Alsothe particular organic compound RX or catalyst promoter also has an influence upon the amount of alkali metal necessary for etlicient operation of the process.

in general from about 0.05 to about 0.5 atomic proportions of alkali metal is present per molar proportion of alkylaromatic hydrocarbon or other side chain alkylatable hydrocarbon present in the reaction zone. Also from about 0.01 to about 0.4 molar-proportion of an RX compound or a mixture of RX compounds disclosed hereinabove will be employed together with the alkali metal. In the resultant catalyst mixture, the alkali metal is present in an amount such that more than one atomic proportion of alkali metal is present per molar proportion of RX compound also utilized in the catalyst.

The ratios within the above defined limits of the alkali metal used and the RX compound are not critical; they will depend upon experimental condition and the compoundsundergoing side chain alkylation.

In carrying out the process the olenic hydrocarbon" charged such as ethylene may be introduced continuously or intermittently, the latter method being commonly employed in the usual type of batch operation conducted in an autoclave so that the consumption of ethylene can be followed by observing the decrease in operating pressure of the autoclave as the reaction progresses. After the reaction has reached the desired stage of completion, the reaction products are discharged from the autoclave, unconverted olefins such as ethylene is recovered for further use in the process or utilized for some other purpose. The mixture of reaction products is then subjected to suitable separation treatment such as filtration to remove unconsumed alkali metal catalyst followed by fractional distillation of normally liquid products to separate unconverted charging stock from side chain alkylated products and higher boiling materials, the latter being sometimes formed as by-products of the reaction.

In this process one molecular proportion of olefin such as ethylene and one molecular proportion of alkylaromaticmatic hydrocarbon as illustrated by the following equatiorr:

C a telys t Toluene Ethylene The resultant reaction product such as n-propylbenzene may sometimes react with a further molecular proportion of olefin as ethylene to form a still longer chain alkylaron-propylbeuzene As can be seen from the table side chain ethylation if it occurred at all, yielded 1.6 grams of product. Neither normal'propylbenzene nor 3-phenylpentane were observed in the product. EXAMPLE H Table II EFFECT OF ALCOHOLS UPON THE SIDE CHAIN ETHYLATION F TOLUENE IN THE PRESENCE OF SODIUM Initial TOL Yield, Moi Percent Sodium Dura' acted Run No. Gms :tEi{on, Mo] 1 3 h I rs. n-propy -p eny- Kind Grams Percent benzene penmne sec-butyl alcohol.... 2. 0 7. 4 5.0 13 iso-butyl alcohol. 2. 0 7. 2 4. 2 19 tert-butyl alcohol... 2.0 6. 7 4. 22 cyclo-hexanol 2. 0 7. 3 5. 0 13 allyl alcoho1. 2.0 7. 3 4. 5 bcnzyl alcohol 2. O 7. 3 3. 5 13 tri-phenyl carbinol. 3. 0 7. 0 5 8 1 The yield was calculated on toluene reacted.

matic hydrocarbon as indicated in the following equation:

Catalyst n-propylbenzene ethylene 3-phenylpcntane EXAMPLE I I A glass-lined rotatable steel autoclave of 850 cc. capacity was charged with 92 grams of toluene and 10 grams of sodium. The autoclave was then closed and ethylene was introduced to the autoclave to an initial pressure of atmospheres. The autoclave containing the toluene, sodium, and ethylene was then rotated and heated for three hours at a temperature of ZOO-325 C. after which the autoclave was permitted to cool to room temperature. The residual ethylene was then discharged from theautoclave. The mixture of liquid products and used sodium was filtered to remove the sodium therefrom and the filtrate was subjected to fractional distillation. The distillation separated the liquid products into fractions with the properties shown in Table I:

Table l FRAOTIONAL DISTILLATION OF REACTION PRODUCTS FROM ETHYLATION OF TOLUENE WITH SODIUM ALONE As an example, the distillation of the reaction product of Run No. 3 is presented in the following Table III:

Table III FRACTIONAL DISTILLATION O1 REACTION PRODUCTS FROM RUN 3 Boiling Point, Grams 71x Composition 104-108 6.2 1.4948 Toluene. 108-110 63.1 1.4962 DO. 110-154 4. 2 1.4928 Mixture of toluene and n-propylbenzcne. 154-156 9.0 1. 4924 n-Propylbenzenc. 156-179 3.7 1,4913 Mixture of n-propylbenzcnc and i l-phenylpcntaue. 179+ 0.7 1.5025 Bottoms.

From the above experiments, it seems that the degree of side chain ethylation depends upon the type of alcohol used. Tert-butyl alcohol promoted the highest conversion of toluene to n-propylbenzene per pass.

EXAMPLE III Essentially the same procedure was employed as in the preceding examples. The glass-lined autoclave of 850 cc. capacity was charged with 92 grams of toluene, 6.9 grams of sodium, 2 grams of nitrobenzene, and enough ethylene to give an initial pressure of 30 atmospheres at a temperature of 20 C. The charged autoclave was then rotated and heated at a temperature of ZOO-226 C. for a time of 5% hours. On working up the product, it was found that 14.6 grams of toluene reacted, forming 12.1 grams of n-propylbenzene. The yield of n-propylbenzene based on toluene reacted was 63 mol per cent.

EXAMPLE IV In another run, 92 grams of toluene, 7.7 grams of sodium, 2.7 gramsof isoamylnitrate, and ethylene (initial pressure 30 atmospheres) were reacted in a rotating steel autoclave at a temperature of ZOO-228 C. for a time of 5 hours. About 7.2 grams of toluene reacted, forming 2.9 grams of n-propylbenzeue, a yield of 25% based upon toluene which reacted.

9 EXAMPLE v Essentially the same procedure as used in the preceding runs was employed in the following runs referred to in Table IV. In the runs in Table IV, 92 grams of toluene was reacted with ethylene (30 atmospheres at room temperature) in the presence of about 7.5 grams (0.34 mol) of sodium and 0.02 mol of m-cresol, o-toluic acid, m-methoxy toluene, and isovaleric acid, respectively:

Table IV SIDE CHAIN ALKYLATION OF TOLUENE IN THE PRESENCE OF SODIUM AND MISCELLANEOUS PROMOTERS Run No 1 2 3 4 Promoter:

Kind m-eresol otoluie acid... m-methoxy lso-valeric toluene acid. Grams- 2.0 2.5 2.0. Sodium, (3111s-. 7 7.1. Temp, C..

Duration, Hrs

Toluene Reaeted, Mol Percent Yield, Mol Percent:

n-Propylbenzene 3-Pheny1pentane l The yields were based on toluene reacted.

Of the promoters referred to in Table IV, o-toluic acid was the most active. In run 2, 53% of the toluene reacted and yielded 60 mol per cent of n-propylbenzene and 21 mol per cent or" 3-phenylpentane.

EXAMPLE VI In another run, using the same procedure as used in the preceding examples, 92 grams of toluene, 7.3 grams of sodium, 2.0 grams of benzonitrile, and ethylene (initial pressure 30 atmospheres) were reacted in a rotating steel autoclave at a temperature of 200-206 C. for a time of 4.5 hours. About 42 mol per cent (38.4 grams) of the toluene reacted yielding 67% normal propylbenzene based on toluene reacted, and 14% 3-phenylpentane based on toluene reacted.

We claim as our invention:

1. In a process which comprises reacting a non-conjugated olefinic hydrocarbon and an aromatic compound selected from the group consisting of carbocyclic aromatic and heterocyclic aromatic ring compounds having attached to a nuclear carbon atom a carbon atom of a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, a cycloalkalkyl group and an aralkyl group and to which last-named carbon atom is attached at least one hydrogen atom, the improvement which comprises carrying out the reaction at a temperature from about 100 to about 350 C. and at a pressure of from about to about 50 atmospheres in the presence of free alkali metal and of an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group, and recovering the resultant condensation product.

2. In a process which comprises reacting a non-conjugated olefinic hydrocarbon and an aromatic compound selected from the group consisting of carbocyclic aromatic and heterocyclic aromatic ring compounds having attached to a nuclear carbon atom a carbon atom of a 6 saturated hydrocarbon group and to which last-named carbon atom is attached at least one hydrogen atom, the improvement which comprises carrying out the reaction at a temperature from about 100 to about 350 C. and at a pressure of from about 5 to about 50 atmospheres in the presence of free alkali metal and of an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic 5 to about atmospheres in the presence of free alkali metal and of an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group.

4. A process for producing longer chain aromatic hydrocarbons which comprises reacting an alkene and an aromatic hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature of from about to about 350 C. and at a pressure of from about 5 to about 50 atmospheres in the presence of free alkali metal and of an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group.

5. A process for producing a longer chain benzene hydrocarbon which comprises reacting an alkene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature of from about 100 to about 350 C. and at a pressure of from about 5 to about 50 atmospheres in the presence of a catalyst comprising essentially free sodium and an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group and a cyano group.

6. A process for producing a longer chain benzene hydrocarbon which comprises reacting ethylene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon ground and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature of from about 100 to about 350 C. and at a pressure of from about 5 to about 50 atmospheres in the presence of a catalyst comprising essentially free alkali metal and an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group, and recovering a longer chain benzene hydrocarbon from the resultant reaction product.

7. A process for producing a longer chain benzene hydrocarbon which comprises reacting ethylene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature of from about 100 to about 350 C. and at a pressure of from about to about 50 atmospheres in the presence of a catalyst comprising essentially free sodium and an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group, and recovering a longer chain benzene hydrocarbon from the resultant reaction products.

8. A process for producing normal propylbenzene which comprises reacting ethylene and toluene at a condensation temperature of from about 100 to about 350 C. and at a pressure of from about 5 to about 50 atmosphere in the presence of a catalyst comprising essentially free sodium and a branched chain alcohol, and recovering normal propylbenzene from the resultant reaction product.

9. A process for producing a longer chain benzene hydrocarbon which comprises reacting ethylene and toluene at a temperature of from about 100 to about 350 C. and at a pressure of from about 5 to about 50 atmospheres in the presence of a catalyst comprising essentially free alkali metal and an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group, and recovering a longer chain benzene hydrocarbon from the resultant reaction product.

10. A process for producing normal propylbenzene which comprises reacting ethylene and toluene at a temperature of from about 100 to about 350 C. and at a pressure of from about 5 to about 50 atmospheres in the presence of a catalyst comprising essentially free sodium and a phenol, and recovering normal propylbenzene from the resultant reaction product.

11. In a process which comprises reacting ethylene and an aromatic compound selected from the group consisting of carbocyciic aromatic and heterocyclic aromatic ring compounds having attached to a nuclear carbon atom a carbon atom of a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, a cycloalkalkyl group and an aralkyl group and to which last named carbon is attached at least one hydrogen atom, the improvement which comprises carrying out the reaction at a temperature from about 100 to about 350 C. and at a pressure of from about 5 to about 50 atmospheres in the presence of free alkali metal and of an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group, and recovering the resultant condensation product.

12. In a process which comprises reacting ethylene and an aromatic compound selected from the group consisting of carbocyclic aromatic and heterocyclic aromatic ring compounds having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom, the improvement which comprises carrying out the reaction at a temperature from about to about 350 C. and at a pressure of from about 5 to about 50 atmospheres in the presence of free alkali metal and of an organic compound represented by the iormula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, 2. nitro group and a cyano group.

13. A process which comprises reacting ethylene and an aromatic compound having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a temperature from about ;00 to about 350 C. and at a pressure of from about 5 to about 50 atmospheres in the presence of free alkali metal and of an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid roup, an alkoxyl group, a nitro group, and a cyano group.

14. A process for producing a longer chain aromatic hydrocarbon which comprises reacting ethylene and an aromatic hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature of from about 100 to about 350 C. and at a pressure of from about 5 to about 50 atmospheres in the presence of free alkali metal and of an organic compound represented by the formula RX wherein R is a member of the group consisting of alkyl, alkenyl, cycloalkyl, aralkyl, and aryl radicals and X is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an alkoxyl group, a nitro group, and a cyano group.

References ited in the file of this patent UNITED STATES PATENTS 2,448,641 Whitman Sept. 7, 1948 2,548,803 Little, Jr. Apr. 10, 1951 2,670,390 Pines et al Feb. 23, 1954 2,688,044 Pines et al Aug. 31, 1954 

1. IN A PROCESS WHICH COMPRISES REACTING A NON-CONJUGATED OLEFINIC HYDROCARBON AND AN AROMATIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF CARBOCYCLIC AROMATIC AND HETEROCYLIC AROMATIC RING COMPOUNDS HAVING ATTACHED TO A NUCLEAR CARBON ATOM A CARBON ATOM OF A HYDROCARBON GROUP SELECTED FROM THE GROUP CONSISTING OF AN ALKYL GROUP, A CYCLOALKYL GROUP, A CYCLOAKALKYL GROUP AND AN ARALKYL GROUP AND TO WHICH LAST-NAMED CARBON ATOM IS ATTACHED AT LEAST ONE HYDROGEN ATOM, THE IMPROVEMENT WHICH COMPRISES CARRYING OUT THE REACTION AT A TEMPERATURE FROM ABOUT 100* TO ABOUT 350* C. AND AT A PRESSURE OF FROM ABOUT 5 TO ABOUT 50 ATMOSPHERES IN THE PRESENCE OF FREE ALKALI METAL AND OF AN ORGANIC COMPOUND REPRESENTED BY THE FORMULA RX WHEREIN R IS A MEMBER OF THE GROUP CONSISTING OF ALKYL, ALKENYL, CYCLOALKYL, ARALKYL, AND ARYL RADICALS AND X IS SELECTED FROM THE GROUP CONSISTING OF A HYDROXYL GROUP, A CARBOXYLIC ACID GROUP, AN ALKOXYL GROUP, A NITRO GROUP, AND A CYANO GROUP, AND RECOVERING THE RESULTANT CONDENSATION PRODUCT. 